Composition and method for improving plant health

ABSTRACT

The present invention relates to plant-protecting active ingredient mixtures comprising, as active components, a neonicotinoid and one or two fungicides selected from pyraclostrobin and boscalid, in synergistically effective amounts and to a method of improving the health of plants by to the plants or the locus thereof by applying said mixtures.

This application is a National Stage application of InternationalApplication No. PCT/EP2006/060103, filed Feb. 20, 2006, which claims thebenefit of U.S. Provisional Application No. 60/655,208, filed Feb. 22,2005, the entire contents of which are hereby incorporated herein byreference.

The present invention relates to plant-protecting active ingredientmixtures having synergistically enhanced action and to a method ofimproving the health of plants by applying said mixtures to the plantsor the locus thereof.

One typical problem arising in the field of pest control lies in theneed to reduce the dosage rates of the active ingredient in order toreduce or avoid unfavorable environmental or toxicological effectswhilst still allowing effective pest and pathogen control.

Another problem encountered concerns the need to have available pestcontrol agents which are effective against a broad spectrum of pests andpathogens.

Another problem underlying the present invention is the desire forcompositions that improve plants, a process which is commonly andhereinafter referred to as “plant health”. For example, advantageousproperties that may be mentioned are improved crop characteristicsincluding: emergence, crop yields, protein content, more developed rootsystem (improved root growth), tillering increase, increase in plantheight, bigger leaf blade, less dead basal leaves, stronger tillers,greener leaf color, pigment content, photosynthetic activity, lessfertilizers needed, less seeds needed, more productive tillers, earlierflowering, early grain maturity, less plant verse (lodging), increasedshoot growth, enhanced plant vigor, increased plant stand and earlygermination; or any other advantages familiar to a person skilled in theart.

Another difficulty in relation to the use of pesticides is that therepeated and exclusive application of an individual pesticidal compoundleads in many cases to a rapid selection of pests or pathogens that havedeveloped natural or adapted resistance against the active compound inquestion.

It was therefore an object of the present invention to providepesticidal mixtures which solve the problems outlined above.

The combating of harmful phytopathogenic fungi is not the only problemthe farmer has to face. Also harmful insects and other pests can cause agreat damage to crops and other plants. An efficient combination offungicidal and insecticidal activity is desirable to overcome thisproblem. Thus, it is a further object of the present invention toprovide a mixture that, on the one hand, has good fungicidal activity,and, on the other hand, good insecticidal activity, resulting in abroader pesticidal spectrum of action.

We have found that this object is in part or in whole achieved by thecombination of active compounds defined at the outset.

Especially, it has been found that a mixture of a neonicotinoid,preferably acetamiprid, clothianidin, dinotefuran, imidacloprid,nitenpyram, thiacloprid or thiamethoxam, more preferably acetamiprid,clothianidin, imidacloprid or thiamethoxam most preferably thiamethoxamand one or two fungicides selected from pyraclostrobin and boscalidachieves and mixtures comprising boscalid and metalaxyl show markedlyenhanced action against plant pathogens compared to the control ratesthat are possible with the individual compounds and/or is suitable forimproving the health of plants when applied to plants, parts of plants,seeds, or at their locus of growth.

Mixtures of thiamethoxam with certain strobilurine fungicides are knownfrom WO99/48366. However, all of the strobilurines mentioned in thatdocument are acetic acid derivatives, whereas pyraclostrobin of thepresent invention is a methyl carbamate.

WO02/102148 discloses mixtures of fludioxonil, metalaxyl and astrobilurine fungicide which optionally may further contain aninsecticide, inter alia thiamethoxam. The strobilurine fungicidesdisclosed all are acetic acid derivatives.

In WO 00/28825, at least quaternary compositions are described thatcomprise an insecticide such as thiamethoxam and three fungicidesselected from acylalanines, for example metalaxyl, phenylpyrroles, forexample fludioxonil, and triazoles, for example difenoconazole.Preferred is a composition comprising thiamethoxam, mefenoxam,fludioxonil and difenoconazole.

None of this documents mentions mixtures of thiamethoxam withpyraclostrobin or boscalid or mixtures comprising boscalid andmetalaxyl.

-   Acetamiprid is an insecticide. See, for example, the Pesticide    Manual, 13th Ed. (2003), The British Crop Protection Council,    London, page 7.-   Clothianidin is an insecticide. See, for example, the Pesticide    Manual, 13th Ed. (2003), The British Crop Protection Council,    London, page 198.-   Dinotefuran is an insecticide. See, for example, the Pesticide    Manual, 13th Ed. (2003), The British Crop Protection Council,    London, page 336.-   Imidacloprid is an insecticide. See, for example, the Pesticide    Manual, 13th Ed. (2003), The British Crop Protection Council,    London, page 562.-   Nitenpyram is an insecticide. See, for example, the Pesticide    Manual, 13th Ed. (2003), The British Crop Protection Council,    London, page 705.-   Thiacloprid is an insecticide. See, for example, the Pesticide    Manual, 13th Ed. (2003), The British Crop Protection Council,    London, page 958.-   Thiamethoxam is an insecticide. See, for example, the Pesticide    Manual, 13th Ed. (2003), The British Crop Protection Council,    London, page 960.-   Pyraclostrobin is a fungicide. See, for example, the Pesticide    Manual, 13th Ed. (2003), The British Crop Protection Council,    London, page 842.-   Boscalid is a fungicide. See, for example, the Pesticide Manual,    13th Ed. (2003), The British Crop Protection Council, London, page    104.-   Fludioxonil is a fungicide. See, for example, the Pesticide Manual,    11th Ed. (1997), The British Crop Protection Council, London, page    566.

Metalaxyl is a fungicide including: metalaxyl; metalaxyl consisting ofmore than 70% by weight of the R-enantiomer; metalaxyl consisting ofmore than 85% by weight of the R-enantiomer; metalaxyl consisting ofmore than 92% by weight of the R-enantiomer; metalaxyl consisting ofmore than 97% by weight of the R-enantiomer; and mefenoxam (i.e.,R-metalaxyl or metalaxyl-M) wherein the metalaxyl component is pureR-metalaxyl which is substantially free of S-enantiomer. See, forexample, the Pesticide Manual, 11th Ed. (1997), The British CropProtection Council, London, page 792; and the Pesticide Manual, 11th Ed.(1997), The British Crop Protection Council, London, page 794.Preferably, the term metalaxyl as used herein refers to mefenoxam.

Preferred are mixtures comprising a neonicotinoid and pyraclostrobin,preferably

acetamiprid and pyraclostrobin,

clothianidin and pyraclostrobin,

dinotefuran and pyraclostrobin,

imidacloprid and pyraclostrobin,

nitenpyram and pyraclostrobin,

thiacloprid and pyraclostrobin,

or thiamethoxam and pyraclostrobin, more preferably mixtures comprising

acetamiprid and pyraclostrobin,

clothianidin and pyraclostrobin,

imidacloprid and pyraclostrobin, or

thiamethoxam and pyraclostrobin, wherein most preferred are mixturescomprising

thiamethoxam and pyraclostrobin.

Preferred are furthermore mixtures comprising a neonicotinoid andboscalid, preferably

acetamiprid and boscalid,

clothianidin and boscalid,

dinotefuran and boscalid,

imidacloprid and boscalid,

nitenpyram and boscalid,

thiacloprid and boscalid,

or thiamethoxam and boscalid, more preferably mixtures comprising

acetamiprid and boscalid,

clothianidin and boscalid,

imidacloprid and boscalid, or

thiamethoxam and boscalid, wherein mixtures comprising thiamethoxam andboscalid are most preferred.

Another preferred embodiment of the present invention comprises mixturescomprising a neonicotinoid, pyraclostrobin and boscalid, preferably

acetamiprid, pyraclostrobin and boscalid,

clothianidin, pyraclostrobin and boscalid,

dinotefuran, pyraclostrobin and boscalid,

imidacloprid, pyraclostrobin and boscalid,

nitenpyram, pyraclostrobin and boscalid,

thiacloprid, pyraclostrobin and boscalid,

or thiamethoxam, pyraclostrobin and boscalid, more preferably mixturescomprising

acetamiprid, pyraclostrobin and boscalid,

clothianidin, pyraclostrobin and boscalid,

imidacloprid, pyraclostrobin and boscalid, or

thiamethoxam, pyraclostrobin and boscalid, wherein most preferred aremixtures comprising

thiamethoxam, pyraclostrobin and boscalid.

The mixtures of the present invention may further comprise metalaxyl.

Accordingly, preferred mixtures comprise a neonicotinoid, pyraclostrobinand metalaxyl, preferably

acetamiprid, pyraclostrobin and metalaxyl,

clothianidin, pyraclostrobin and metalaxyl,

dinotefuran, pyraclostrobin and metalaxyl,

imidacloprid, pyraclostrobin and metalaxyl,

nitenpyram, pyraclostrobin and metalaxyl,

thiacloprid, pyraclostrobin and metalaxyl,

or thiamethoxam, pyraclostrobin and metalaxyl, more preferably mixturescomprising

acetamiprid, pyraclostrobin and metalaxyl,

clothianidin, pyraclostrobin and metalaxyl,

imidacloprid, pyraclostrobin and metalaxyl, or

thiamethoxam, pyraclostrobin and metalaxyl, wherein most preferred aremixtures comprising thiamethoxam, pyraclostrobin and metalaxyl.

Furthermore, preferred mixtures comprise a neonicotinoid, boscalid andmetalaxyl, preferably

acetamiprid, boscalid and metalaxyl,

clothianidin, boscalid and metalaxyl,

dinotefuran, boscalid and metalaxyl,

imidacloprid, boscalid and metalaxyl,

nitenpyram, boscalid and metalaxyl,

thiacloprid, boscalid and metalaxyl,

or thiamethoxam, boscalid and metalaxyl, more preferably mixturescomprising

acetamiprid, boscalid and metalaxyl,

clothianidin, boscalid and metalaxyl,

imidacloprid, boscalid and metalaxyl, or

thiamethoxam, boscalid and metalaxyl, wherein most preferred aremixtures comprising thiamethoxam, boscalid and metalaxyl are preferred.

In another preferred embodiment of the present invention, preferredmixtures comprise a neonicotinoid, pyraclostrobin, boscalid, andmetalaxyl, preferably

acetamiprid, boscalid, pyraclostrobin and metalaxyl,

clothianidin, boscalid, pyraclostrobin and metalaxyl,

dinotefuran, boscalid, pyraclostrobin and metalaxyl,

imidacloprid, boscalid, pyraclostrobin and metalaxyl,

nitenpyram, boscalid, pyraclostrobin and metalaxyl,

thiacloprid, boscalid, pyraclostrobin and metalaxyl,

or thiamethoxam, boscalid, pyraclostrobin and metalaxyl, morepreferrably mixtures comprising

acetamiprid, boscalid, pyraclostrobin and metalaxyl,

clothianidin, boscalid, pyraclostrobin and metalaxyl,

imidacloprid, boscalid, pyraclostrobin and metalaxyl, or

thiamethoxam, boscalid, pyraclostrobin and metalaxyl, wherein mostpreferred are mixtures comprising thiamethoxam, pyraclostrobin, boscalidand metalaxyl.

Another preferred embodiment of the present invention comprises mixturescomprising boscalid and metalaxyl

All embodiments of the above-mentioned mixtures are herein below alsoreferred to as “inventive mixtures” or “mixtures according to theinvention”.

The inventive mixtures are suitable for foliar application in livingcrops of plants as well as, in particular, for dressing applications onplant propagation material. The latter term embraces seeds of all kinds(fruit, tubers, grains), cuttings, cut shoots and the like. Oneparticular field of application is the treatment of all kinds of seeds.

In addition to the mixtures, this invention also relates to a method ofcontrolling fungi and/or improving the health of plants, which comprisestreating a site, for example a plant or a plant propagation material,that is infested or liable to be infested by fungi with a) aneonicotinoid, preferably acetamiprid, clothianidin, dinotefuran,imidacloprid, nitenpyram, thiacloprid or thiamethoxam, more preferablyacetamiprid, clothianidin, imidacloprid or thiamethoxam most preferablythiamethoxam, with b) pyraclostrobin, and/or with c) boscalid, in anydesired sequence or simultaneously, that is, jointly or separately.

In addition, the invention furthermore relates to a method ofcontrolling fungi and/or improving the health of plants, which comprisestreating a site, for example a plant or a plant propagation material,that is infested or liable to be infested by fungi with a) boscalid andb) metalaxyl, in any desired sequence or simultaneously, that is,jointly or separately.

Generally, the invention furthermore relates to a method of controllingfungi and/or improving the health of plants, which comprises treating asite, for example a plant or a plant propagation material, that isinfested or liable to be infested by fungi with the pesticides presentin a inventive mixture in any desired sequence or simultaneously, thatis, jointly or separately.

Advantageous mixing ratios by weight of the active ingredients areneonicotinoid, preferably acetamiprid, clothianidin, dinotefuran,imidacloprid, nitenpyram, thiacloprid or thiamethoxam, more preferablyacetamiprid, clothianidin, imidacloprid or thiamethoxam most preferablythiamethoxam:pyraclostrobin or :boscalid from 100:1 to 1:100. Apreferred ratio for neonicotinoid, preferably acetamiprid, clothianidin,dinotefuran, imidacloprid, nitenpyram, thiacloprid or thiamethoxam, morepreferably acetamiprid, clothianidin, imidacloprid or thiamethoxam mostpreferably thiamethoxam:boscalid is 10:1 to 1:10. For example, for seedtreatment, ratios of 3 kg:30 g a.i./100 kg, 100 g:1 g a.i./100 kg, 30g:3 kg a.i./100 kg or 1 g:10 g a.i./100 kg of seed are suitable. Forsome specific crop seeds, such as lettuce or onions, the rates can behigher.

Furthermore, advantageous mixing ratios by weight of three activeingredients are thiamethoxam:pyraclostrobin:boscalid in which eachcombination of two ingredients in the mixture of three ingredientsranges from 100:1 to 1:100. The amount of any one of the ingredients inthe mixture may range from 1 g to 3 kg a.i./100 kg of seed. For example,ratios of 50 g:5 g:20 g a.i./100 kg is suitable.

Advantageously, the pesticidal mixtures may comprise metalaxyl in whicheach combination of two ingredients in the mixture of two to fouringredients ranges from 100:1 to 1:100.

Advantageous mixing ratios by weight of the active ingredients aremetalaxyl:boscalid from 100:1 to 1:100 by weight.

The novel active ingredient mixtures have very advantageous curative,preventive and systemic fungicidal properties for protecting cultivatedplants. As has been mentioned, said active ingredient mixtures can beused to inhibit or destroy the pathogens that occur on plants or partsof plants (fruit, blossoms, leaves, stems, tubers, roots) of differentcrops or useful plants, while at the same time those parts of plantswhich grow later are also protected from attack by such pathogens.Active ingredient mixtures have the special advantage of being highlyactive against diseases in the soil that mostly occur in the earlystages of plant development.

Specifically, they are suitable for controlling the following harmfulfungi:

-   -   Alternaria species on vegetables and fruit,    -   Bipolaris and Drechslera species on cereals, rice and turf,    -   Blumeria graminis (powdery mildew) on cereals,    -   Botrytis cinerea (gray mold) on strawberries, vegetables,        ornamentals and grapevines,    -   Didymella species on various plants,    -   Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,    -   Fusarium and Verticillium species on various plants,    -   Mycosphaerella species on cereals, bananas and peanuts,    -   Phakopsara pachyrhizi and Phakopsara meibomiae on soybeans    -   Phytophthora species on various plants,    -   Plasmopara viticola on grapevines,    -   Podosphaera leucotricha on apples,    -   Pseudocercosporella herpotrichoides on wheat and barley,    -   Pseudoperonospora species on hops and cucumbers,    -   Puccinia species on cereals,    -   Pyricularia oryzae on rice,    -   Pythium species on various plants,    -   Rhizoctonia species on cotton, legumes, rice and turf,    -   Sclerotinia species on various plants,    -   Septoria tritici and Stagonospora nodorum on wheat,    -   Thielaviopsis species on various plants,    -   Uncinula necator on grapevines,    -   Ustilago species on cereals and sugar cane, and    -   Venturia species (scab) on apples and pears.

The mixtures, which comprise a neonicotinoid are also suitable forcontrolling the following harmful insects from the order of the

lepidopterans (Lepidoptera), for example Agrotis ypsilon, Agrotissegetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthiaconjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana,Capua reticulana, Chematobia brumata, Choristoneura fumiferana,Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella,Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Eariasinsulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetriabouliana, Feltia subterranea, Galleria mellonella, Grapholithafunebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens,Heliothis zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea,Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria,Laphygma exigua, Leucoptera coffeella, Leucoptera scitella,Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis,Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosomaneustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis,Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalerabucephala, Phthorimaea operculella, Phyllocnistis citrella, Pierisbrassicae, Plathypena scabra, Plutella xylostella, Pseudoplusiaincludens, Rhyacionia frustrana, Scrobipalpula absoluta, Sitotrogacerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodopteralittoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrixviridana, Trichoplusia ni and Zeiraphera canadensis,beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus,Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar,Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophaguspiniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum,Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotomatrifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnematibialis, Conoderus vespertinus, Crioceris asparagi, Diabroticalongicornis, Diabrotica speciosa, Diabrotica 12-punctata, Diabroticavirgifera, Diloboderus abderus, Epilachna varivestis, Epitrixhirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hyperabrunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lemamelanopus, Leptinotarsa decemlineata, Limonius californicus,Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus,Melolontha hippocastani, Melolontha melolontha, Oulema oryzae,Ortiorrhynchus sulcatus, Oryazophagus oryzae, Otiorrhynchus ovatus,Phaedon cochleariae, Phyllotreta chrysocephala, Phyllophaga sp.,Phyllophaga cuyabana, Phyllophaga triticophaga, Phyllopertha horticola,Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitonalineatus and Sitophilus granaria,dipterans (Diptera), for example Aedes aegypti, Aedes vexans, Anastrephaludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana,Chrysomya hominivorax, Chrysomya macellaria, Contarinia sorghicola,Cordylobia anthropophaga, Culex pipiens, Dacus cucurbitae, Dacus oleae,Dasineura brassicae, Fannia canicularis, Gasterophilus intestinalis,Glossina morsitans, Haematobia irritans, Haplodiplosis equestris,Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyzatrifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoriapectoralis, Mayetiola destructor, Musca domestica, Muscina stabulans,Oestrus ovis, Oscinella frit, Pegomya hysocyami, Phorbia antiqua,Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi, Rhagoletispomonella, Tabanus bovinus, Tipula oleracea and Tipula paludosa,thrips (Thysanoptera), e.g. Frankliniella fusca, Frankliniellaoccidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae,Thrips palmi and Thrips tabaci,hymenopterans (Hymenoptera), e.g. Acromyrmex ambuguus, Acromyrmexcrassispinus, Acromyrmex heiery, Acromyrmex landolti, Acromyrmexsubterraneus, Athalia rosae, Atta capiguara, Atta cephalotes, Attalaevigata, Atta robusta, Atta sexdens, Atta texana, Hoplocampa minuta,Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata andSolenopsis invicta,heteropterans (Heteroptera), e.g. Acrosternum hilare, Blissusleucopterus, Cyrtopeltis notatus, Dichelops furcatus, Dysdercuscingulatus, Dysdercus intermedius, Euchistos heros, Eurygasterintegriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lyguslineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata,Piezodorus guildini, Solubea insularis and Thyanta perditor,Hemiptera and Homoptera, e.g. Acrosternum hilare, Blissus leucopterus,Cyrtopeltis notatus, Diaphorina citri, Dysdercus cingulatus, Dysdercusintermedius, Eurygaster integriceps, Euschistus impictiventris,Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezaraviridula, Piesma quadrata, Solubea insularis, Thyanta perditor,Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphisfabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae,Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum,Aulacorthum solani, Brachycaudus cardui, Brachycaudus helichrysi,Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne brassicae,Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii,Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphisradicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphispyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactucae,Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megouraviciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzodes persicae,Myzus ascalonicus, Myzus cerasi, Myzus varians, Nasonovia ribis-nigri,Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida,Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus,Rhopalosiphum maidis, Rhopalosiphum padi, Rhopalosiphum insertum,Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneuralanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxopteraaurantiiand, Viteus vitifolii, Cimex lectularius, Cimex hemipterus,Reduvius senilis, Triatoma spp., and Arilus critatus,termites (Isoptera), e.g. Calotermes flavicollis, Cornitermes cumulans,Heterotermes tenuis, Leucotermes flavipes, Neocapritemes opacus,Procornitermes triacifer; Reticulitermes lucifugus, Syniormes molestus,and Termes natalensis,orthopterans (Orthoptera), e.g. Acheta domestica, Blatta orientalis,Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa,Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum,Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus,Nomadacris septemfasciata, Periplaneta americana, Schistocercaamericana, Schistocerca peregrina, Stauronotus maroccanus and Tachycinesasynamorus,Arachnoidea, such as arachnids, e.g. of the families Argasidae, Ixodidaeand Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum,Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilusmicroplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus,Ixodes rubicundus, Ornithodorus moubata, Otobius megnini, Dermanyssusgallinae, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalusevertsi, Sarcoptes scabiei, and Eriophyidae spp. such as Aculusschlechtendali, Phyllocoptrata oleivora and Eriophyes sheldoni;Tarsonemidae spp. such as Phytonemus pallidus and Polyphagotarsonemuslatus; Tenuipalpidae spp. such as Brevipalpus phoenicis; Tetranychidaespp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychuspacificus, Tetranychus telarius and Tetranychus urticae, Panonychusulmi, Panonychus citri, and oligonychus pratensis;thrips (Thysanoptera), e.g. Frankliniella fusca, Frankliniellaoccidentalis, Frankliniella schultzei, Frankliniella tritici,Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci.

In particular, the inventive mixtures are suitable for combating pestsof the orders Coleoptera, Lepidoptera, Thysanoptera, Homoptera,Isoptera, and Orthoptera.

They are also suitable for controlling the following plant parasiticnematodes such as Meloidogyne, Globodera, Heterodera, Radopholus,Rotylenchulus, Pratylenchus and other genera.

Suitable targets for seed treatment are various crop seeds, fruitspecies, vegetables, spices and ornamental seed, for example corn/maize(sweet and field), durum wheat, soybean, wheat, barley, oats, rye,triticale, bananas, rice, cotton, sunflower, potatoes, pasture, alfalfa,grasses, turf, sorghum, rapeseed, Brassica spp., sugar beet, eggplants,tomato, lettuce, iceberg lettuce, pepper, cucumber, squash, melon, bean,dry-beans, peas, leek, garlic, onion, cabbage, carrot, tuber such assugar cane, tobacco, coffee, turf and forage, cruciferous, cucurbits,grapevines, pepper, fodder beet, oil seed rape, pansy, impatiens,petunia and geranium.

The term seed treatment comprises all suitable seed treatment techniquesknown in the art, such as, but not limited to, seed dressing, seedcoating, seed dusting, seed soaking, seed film coating, seed multilayercoating, seed encrusting, seed dripping, and seed pelleting.

The active ingredient mixtures according to the invention are especiallyadvantageous for seed treatment of oil seed rape, wheat, corn, rye,barley, oats, sorghum, sunflowers, rice, maize, turf and forage, sugarbeet, beans, peas, soybeans, ornamentals, and vegetables such ascucurbits, tomatoes, eggplant, potatoes, pepper, lettuce, cabbage,carrots, cruciferous.

Especially preferred is the seed treatment of oil seed rape, wheat,beans, corn, soybeans, sugar beet, rice, vegetables, and ornamentals.

The mixtures according to the invention are most preferably used for theseed treatment of oil seed rape.

In addition, mixtures according to the invention may also be used incrops which tolerate the action of herbicides or fungicides orinsecticides owing to breeding, including genetic engineering methods.

For example, mixtures according to the invention can be employed intransgenic crops which are resistant to herbicides from the groupconsisting of the sulfonylureas, imidazolinones, glufosinate-ammonium orglyphosate-isopropylammonium and analogous active substances (see forexample, EP-A-0242236, EP-A-242246) (WO 92/00377) (EP-A-0257993, U.S.Pat. No. 5,013,659) or in transgenic crop plants, for example cotton,with the capability of producing Bacillus thuringiensis toxins (Bttoxins) which make the plants resistant to certain pests (EP-A-0142924,EP-A-0193259),

Furthermore, mixtures according to the invention can be used also forthe treatment of plants which have modified characteristics incomparison with existing plants consist, which can be generated forexample by traditional breeding methods and/or the generation ofmutants, or by recombinant procedures). For example, a number of caseshave been described of recombinant modifications of crop plants for thepurpose of modifying the starch synthesized in the plants (e.g. WO92/11376, WO 92114827, WO 91/19806) or of transgenic crop plants havinga modified fatty acid composition (WO 91/13972).

In addition, the synergistically enhanced action of the mixturesmanifests itself, for example, in lower rates of application and/or in alonger duration of action and/or higher crop yields. Such enhancementswere not to be expected from the sum of the actions of the individualcomponents.

It has been found that the action of the inventive mixtures, e.g. of themixture of a neonicotinoid, preferably acetamiprid, clothianidin,dinotefuran, imidacloprid, nitenpyram, thiacloprid or thiamethoxam, morepreferably acetamiprid, clothianidin, imidacloprid or thiamethoxam mostpreferably thiamethoxam with pyraclostrobin and/or boscalid goes farbeyond the fungicidal action of the fungicide(s) present in the mixturealone. It has been shown that the mixtures exhibit plant health effects(as outlined above) in the frame of the present invention. The termplant health comprises various sorts of improvements of plants that arenot connected to the control of pests with the said mixture of aneonicotinoid, preferably acetamiprid, clothianidin, dinotefuran,imidacloprid, nitenpyram, thiacloprid or thiamethoxam, more preferablyacetamiprid, clothianidin, imidacloprid or thiamethoxam most preferablythiamethoxam with pyraclostrobin and/or boscalid.

The active ingredient mixtures can be used in the form of premixformulations or the active ingredients can be applied to the area, plantor seed to be treated simultaneously or in immediate succession, ifdesired together with further carriers, surfactants or otherapplication-promoting adjuvants customarily employed in formulationtechnology.

The formulations are prepared in a known manner, for example byextending the active compound with auxiliaries suitable for theformulation of agrochemicals, such as solvents and/or carriers, ifdesired surfactants (e.g. surfactants, adjuvans and/or dispersants),preservatives, antifoaming agents, anti-freezing agents, for seedtreatment formulation also optionally colorants and/or binders and/orgelling agents. (see e.g. for review U.S. Pat. No. 3,060,084, EP-A 707445 (for liquid concentrates), Browning, “Agglomeration”, ChemicalEngineering, Dec. 4, 1967, 147-48, Perry's Chemical Engineer's Handbook,4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and et seq. WO91/13546, U.S. Pat. No. 4,172,714, U.S. Pat. No. 4,144,050, U.S. Pat.No. 3,920,442, U.S. Pat. No. 5,180,587, U.S. Pat. No. 5,232,701, U.S.Pat. No. 5,208,030, GB 2,095,558, U.S. Pat. No. 3,299,566, Klingman,Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961,Hance et al., Weed Control Handbook, 8th Ed., Blackwell ScientificPublications, Oxford, 1989 and Mollet, H., Grubemann, A., Formulationtechnology, Wiley VCH Verlag GmbH, Weinheim (Germany), 2001, 2. D. A.Knowles, Chemistry and Technology of Agrochemical Formulations, KluwerAcademic Publishers, Dordrecht, 1998 (ISBN 0-7514-0443-8).

Solvents/auxiliaries which are suitable include:

-   -   water, aromatic solvents (for example Solvesso products,        xylene), paraffins (for example mineral fractions), alcohols        (for example methanol, butanol, pentanol, benzyl alcohol),        ketones (for example cyclohexanone, gamma-butyrolactone),        pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols,        fatty acid dimethylamides, fatty acids and fatty acid esters. In        principle, solvent mixtures may also be used.    -   carriers such as ground natural minerals (for example kaolins,        clays, talc, chalk) and ground synthetic minerals (for example        highly disperse silica, silicates); emulsifiers such as nonionic        and anionic emulsifiers (for example polyoxyethylene fatty        alcohol ethers, alkylsulfonates and arylsulfonates) and        dispersants such as lignin-sulfite waste liquors and        methylcellulose.

Suitable surfactants are alkali metal, alkaline earth metal and ammoniumsalts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonicacid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkylsulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids andsulfated fatty alcohol glycol ethers, furthermore condensates ofsulfonated naphthalene and naphthalene derivatives with formaldehyde,condensates of naphthalene or of naphthalenesulfonic acid with phenoland formaldehyde, polyoxyethylene octylphenyl ether, ethoxylatedisooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers,tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether,alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene oxidecondensates, ethoxylated castor oil, polyoxyethylene alkyl ethers,ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal,sorbitol esters, lignin-sulfite waste liquors and methylcellulose.

Substances which are suitable for the preparation of directly sprayablesolutions, emulsions, pastes or oil dispersions are mineral oilfractions of medium to high boiling point, such as kerosene or dieseloil, furthermore coal tar oils and oils of vegetable or animal origin,aliphatic, cyclic and aromatic hydrocarbons, for example toluene,xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or theirderivatives, methanol, ethanol, propanol, butanol, cyclohexanol,cyclohexanone, isophorone, strongly polar solvents, for example dimethylsulfoxide, N-methylpyrrolidone and water.

Seed Treatment formulations may additionally comprise binders andoptionally colorants.

Binders can be added to improve the adhesion of the active materials onthe seeds after treatment. Suitable binders are block copolymers EO/POsurfactants but also polyvinylalcohols, polyvinylpyrrolidones,polyacrylates, polymethacrylates, polybutenes, polyisobutylenes,polystyrene, polyethyleneamines, polyethyleneamides, polyethyleneimines(Lupasol®, Polymin®), polyethers, polyurethans and copolymers derivedfrom these polymers.

Optionally, also colorants can be included in the formulation. Suitablecolorants or dyes for seed treatment formulations are Rhodamin B, C.I.Pigment Red 112, C.I. Solvent Red 1, pigment blue 15:4, pigment blue15:3, pigment blue 15:2, pigment blue 15:1, pigment blue 80, pigmentyellow 1, pigment yellow 13, pigment red 112, pigment red 48:2, pigmentred 48:1, pigment red 57:1, pigment red 53:1, pigment orange 43, pigmentorange 34, pigment orange 5, pigment green 36, pigment green 7, pigmentwhite 6, pigment brown 25, basic violet 10, basic violet 49, acid red51, acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10,basic red 108.

An example of a gelling agent is carrageen (Satiagel®)

Powders, materials for spreading and dustable products can be preparedby mixing or concomitantly grinding the active substances with a solidcarrier.

Granules, for example coated granules, impregnated granules andhomogeneous granules, can be prepared by binding the active compounds tosolid carriers. Examples of solid carriers are mineral earths such assilica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk,bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate,magnesium sulfate, magnesium oxide, ground synthetic materials,fertilizers, such as, for example, ammonium sulfate, ammonium phosphate,ammonium nitrate, ureas, and products of vegetable origin, such ascereal meal, tree bark meal, wood meal and nutshell meal, cellulosepowders and other solid carriers.

In general, the formulations comprise from 0.01 to 95% by weight,preferably from 0.1 to 90% by weight, of the active compounds. Theactive compounds are employed in a purity of from 90% to 100%,preferably 95% to 100% (according to NMR spectrum). The following areexamples of formulations: 1. Products for dilution with water for foliarapplication/for seed treatment purposes, these products can be applieddiluted or undiluted.

A) Soluble Concentrates (SL, LS)

10 parts by weight of the active compounds are dissolved in water or ina water-soluble solvent. As an alternative, wetters or other auxiliariesare added. The active compound dissolves upon dilution with water.

B) Dispersible Concentrates (DC)

20 parts by weight of the active compounds are dissolved incyclohexanone with addition of a dispersant, for examplepolyvinylpyrrolidone. Dilution with water gives a dispersion.

C) Emulsifiable Concentrates (EC)

15 parts by weight of the active compounds are dissolved in xylene withaddition of calcium dodecylbenzenesulfonate and castor oil ethoxylate(in each case 5% strength). Dilution with water gives an emulsion.

D) Emulsions (EW, EO, ES)

40 parts by weight of the active compounds are dissolved in xylene withaddition of calcium dodecylbenzenesulfonate and castor oil ethoxylate(in each case 5% strength). This mixture is introduced into water bymeans of an emulsifier (Ultraturax) and made into a homogeneousemulsion. Dilution with water gives an emulsion.

E) Suspensions (SC, OD, FS)

In an agitated ball mill, 20 parts by weight of the active compounds arecomminuted with addition of dispersant, wetters and water or an organicsolvent to give a fine active compound suspension. Dilution with watergives a stable suspension of the active compound.

F) Water-Dispersible Granules and Water-Soluble Granules (WG, SG)

50 parts by weight of the active compounds are ground finely withaddition of dispersants and wetters and made into water-dispersible orwater-soluble granules by means of technical appliances (for exampleextrusion, spray tower, fluidized bed). Dilution with water gives astable dispersion or solution of the active compound.

G) Water-Dispersible Powders and Water-Soluble Powders (WP, SP, WS)

75 parts by weight of the active compounds are ground in a rotor-statormill with addition of dispersant, wetters and silica gel. Dilution withwater gives a stable dispersion or solution with the active compound.

2. Products to be applied undiluted for foliar application. For seedtreatment purposes, these products can be applied diluted or undiluted.

H) Dustable Powders (DP, DS)

5 parts by weight of the active compounds are ground finely and mixedintimately with 95% of finely divided kaolin. This gives a dustableproduct.

I) Granules (GR, FG, GG, MG)

0.5 part by weight of the active compounds is ground finely andassociated with 95.5% carriers. Current methods are extrusion,spray-drying or the fluidized bed. This gives granules to be appliedundiluted.

J) ULV Solutions (UL)

10 parts by weight of the active compounds are dissolved in an organicsolvent, for example xylene. This gives a product to be appliedundiluted.

The active compounds can be used as such, in the form of theirformulations or the use forms prepared therefrom, for example in theform of directly sprayable solutions, powders, suspensions ordispersions, emulsions, oil dispersions, pastes, dustable products,materials for spreading, or granules, by means of spraying, atomizing,dusting, spreading or pouring. The use forms depend entirely on theintended purposes; it is intended to ensure in each case the finestpossible distribution of the active compounds according to theinvention.

Aqueous use forms can be prepared from emulsion concentrates, pastes orwettable powders (sprayable powders, oil dispersions) by adding water.To prepare emulsions, pastes or oil dispersions, the substances, as suchor dissolved in an oil or solvent, can be homogenized in water by meansof a wetter, tackifier, dispersant or emulsifier. Alternatively, it ispossible to prepare concentrates composed of active substance, wetter,tackifier, dispersant or emulsifier and, if appropriate, solvent or oil,and such concentrates are suitable for dilution with water.

The active compound concentrations in the ready-to-use preparations canbe varied within relatively wide ranges. In general, they are from0.0001 to 10%, preferably from 0.01 to 1%.

Various types of oils, wetters, adjuvants, herbicides, fungicides, otherpesticides, or bactericides may be added to the active compounds, ifappropriate just immediately prior to use (tank mix). These agents canbe admixed with the agents according to the invention in a weight ratioof 1:10 to 10:1.

The agrochemical compositions usually comprise 0.1 to 99%, preferably0.1 to 95%, of active ingredients, 99.9 to 1%, preferably 99.9 to 5%, ofa solid or liquid adjuvant, and 0 to 25%, preferably 0.1 to 25%, of asurfactant.

Depending on the desired effect, the application rates of the mixturesaccording to the invention are from 0.1 g/ha to 2000 g/ha, preferablyfrom 50 to 1500 g/ha, in particular from 50 to 750 g/ha.

In the treatment of seed, the application rates of the mixture aregenerally from C. 1 g to 5 kg per 100 kg of seed, preferably from 1 g to2.5 kg per 100 kg of seed, in particular from 1 g to 1 kg per 100 kg ofseed.

In the control of pests, the separate or joint application of theinventive mixtures or compositions comprising them is carried out byspraying or dusting or otherwise applying the mixture to the seeds, theseedlings, the plants or the soils before or after sowing of the plantsor before or after emergence of the plants.

Conventional seed treatment formulations include for example flowableconcentrates FS, solutions LS, powders for dry treatment DS, waterdispersible powders for slurry treatment WS, water-soluble powders SSand emulsion ES and EC, wherein FS and WS are the most preferred ones.

In accordance with one variant, a further subject of the invention is amethod of treating soil by the application, in particular into the seeddrill: either of a granular formulation containing the two activeingredients in combination or as a composition, or of a mixture of twogranular formulations, each containing one of the two activeingredients, with optionally one or more solid or liquid, agriculturallyacceptable carriers and/or optionally with one or more agriculturallyacceptable surfactants. This method is advantageously employed inseedbeds of cereal, maize, cotton and sunflower.

The invention also relates to the propagation products of plants, andespecially the seed comprising, that is treated with a mixture asdefined above or a composition containing the inventive mixture or amixture of compositions each providing one of the active ingredients.

The seed comprises the inventive mixtures in an amount of from 0.1 g to5 kg per 100 kg of seed.

The synergistic pesticidal action of the inventive mixtures can bedemonstrated by the experiments below:

Treatments

Each mixture partner is evaluated separately at the same rates as usedin the mixtures. Synergism is determined by comparing the expectedbiological effect on plant health or on disease control from the mixturebased on the individual effects from the separate partners to thebiological effect seen with the mixture. Abbott's formula can be used tomake this comparison.

Seed Treatment—Cotton

Compounds are used as technical materials and formulated in 15% acetonein 0.05% aqueous Tween 20® (Polyoxyethylene sorbitan monolaurate). Fiftycotton seeds are placed in a 120 ml glass vial and 300 μl of thecompound preparation are pipetted onto the side of the vial just abovethe seeds. The vial can shaken for 3 minutes and the treated seeds wereplaced on aluminum foil to dry.

Plant Health

24 cotton seeds of each treatment are planted, 2 seeds per 7.5 cm squareplastic pot containing Metro Mix 360 planting material and maintained inthe greenhouse. Measurements taken of plant health are time toemergence, percent emergence, shoot biomass and root biomass at the2-true-leaf stage.

Synergistic Plant Disease Control

To determine treatment effects on plant disease control, 12 cotton seedsof each treatment are planted, 2 seeds per 7.5 cm square plastic potcontaining sandy soil and challenged with fungal pathogens. Two fungalpathogens can be used: Pythium sp. and Rhizoctonia sp. Plants aremaintained in the greenhouse with bottom watering. Measurements of theseverity of damping off and root rot are taken and then percent diseasecontrol is calculated for each treatment based on the untreatedcontrols.

The test results will show that the mixtures according to the inventionshow a considerable enhanced activity demonstrating synergism comparedto the calculated sum of the single activities.

Synergistic Plant Health Effects

The synergistic plant health effects of the inventive mixtures has beendemonstrated by the experiments described below:

To determine seed treatment effects of the inventive mixtures on planthealth soft red winter wheat seeds (Variety Coker 9663) were treatedwith mixtures and with each mixture partner separately. Compounds wereapplied in water if formulated or in 25% acetone if technical material.For mixtures, water was used as the carrier unless one or more partnerswas used as technical material then 25% acetone was used as the carrier.Each treatment was prepared in a 20 ml glass vial. Then 25 seeds wereadded, and the vial was vortexed for one minute. After treatment, seedswere allowed to dry.

Plant growth pouches (18 cm×16.5 cm Cyg™ Germination Pouches,Mega-International) were watered with 17-20 ml water, and 4 seeds wereplaced in each growth pouch on the same day as treatment. Replicationwas 4× to 5×. Growth pouches were incubated at 25 C with 14 hours lightand watered as needed. Germination was evaluated at 3-4 and 7-8 daysafter treatment (DAT). Root length and wet weight mass and shoot lengthand wet weight mass were evaluated 7-8 DAT.

Expected responses from the mixture were calculated based on theresponses observed when each mixture partner was applied alone.

Percent effects for each of the mixture partners (MP1 and MP2) appliedsolo were calculated as follows:MP1=(Control response−MP1 response)/Control response*100%MP2=(Control response−MP2 response)/Control response*100%

The appropriate control response was used for each mixture partner.

Then, the expected % response for the mixture was calculated usingAbbott's formula as follows:E % response=(MP1+MP2)−(MP1*MP2)/100

Finally, the expected response for the mixture was calculated byapplying the expected % response to the appropriate control for themixture, which is the solvent blank control, as follows:Expected response=Control response−(Control response*E % response/100)

Experiment 1

For each of the four measures of wheat plant health (root length, rootmass, shoot length, and shoot mass), the actual response observed forthe thiamethoxam plus boscalid mixture (50 g ai+20 g all respectivelyper 100 kg seed) was greater than the expected response based on theresponses observed when each partner was applied alone demonstrating asynergistic effect on plant health. (Table 1).

Percent germination of the wheat seeds for all treatments was 100%.

TABLE 1 Thiamethoxam + Boscalid (50 + 20 g ai/100 kg seed) Wheat PlantExpected Mixture Response Actual Mixture Growth Measurement based onMedian Solo Effects Response Root Length (cm) 14.9 15.5 Root Mass (g)0.044 0.070 Shoot Length (cm) 14.3 15.8 Shoot Mass (g) 0.063 0.067Evaluations were conducted on 20 seedlings per treatment, 5 reps with 4seedlings each.

Experiment 2

For three of the four measures of wheat plant health (root mass, shootlength, shoot mass), the actual response observed for the thiamethoxamand metalaxyl mixture (50 g ai+20 g ai respectively per 100 kg seed) wasgreater than the expected response based on the responses observed wheneach partner was applied alone (Table 2).

Percent germination of the wheat seeds for all treatments was 100%.

Evaluations were conducted on 16 seedlings per treatment, 4 reps with 4seedlings each.

TABLE 2 Thiamethoxam + Metalaxyl (50 + 20 g ai/100 kg seed Wheat PlantExpected Mixture Response Actual Mixture Growth Measurement″ based onMedian Solo Effects Response Root Length (cm) 15.8 15.0 Root Mass (g)0.057 0.066 Shoot Length (cm) 13.6 16.1 Shoot Mass (g) 0.054 0.062Evaluations were conducted on 16 seedlings per treatment, 4 reps with 4seedlings each.

The invention claimed is:
 1. A pesticidal mixture comprising as activecomponents, boscalid and a neonicotinoid selected from the groupconsisting of acetamiprid, thiamethoxam, and clothianidin in a weightratio of from 100:1 to 1:100.
 2. The pesticidal mixture according toclaim 1, wherein the neonicotinoid is thiamethoxam.
 3. A method ofimproving the health of plants, which comprises applying boscalid and aneonicotinoid selected from the group consisting of acetamiprid,thiamethoxam, and clothianidin in a weight ratio of from 100:1 to 1:100,simultaneously, jointly, separately, or in succession.
 4. A method asclaimed in claim 3, wherein the mixture is applied in an amount of from0.1 g/ha to 2000 g/ha.
 5. A method of controlling or preventing fungalor insecticidal infestation in plants, parts of plants, seeds, or attheir locus of growth, which comprises applying boscalid and aneonicotinoid selected from the group consisting of acetamiprid,thiamethoxam, and clothianidin in a weight ratio of from 100:1 to 1:100,simultaneously, jointly, separately, or in succession.
 6. A method ofprotection of seeds comprising contacting the seeds before sowing and/orafter pregermination with the mixture as defined in claim 1 in asynergistically effective amount.
 7. A method as claimed in claim 6wherein the mixture is applied in an amount of from 0.1 g to 5 kg per100 kg of seeds.
 8. A plant propagation material treated with themixtures as defined in claim
 1. 9. The plant propagation material ofclaim 8, wherein seeds are the propagation material.
 10. A seed treatedwith the mixture as claimed in claim 1 in an amount of from 0.1 g to 5kg per 100 kg of seeds.